Blue anthraquinone dye and process of making same.



UNITED STATES Patented July 2s, 1.903.

ATENT FFICE.L

EDUA D HEPP, OF FRANKFORT-ON-THE-MAIN, AND oHRIsToPH HART- MANN, OFHooHsT-o -THE-MAI GERMANY, ASSIGNORS TO FARR- WERKE, voRM. MEISTER,LUCIUS & BRUNING, OF HooHs'r-oN-rHE- MAIN, GERMANY, A CORPORATION OFGERMANY. 1

BLUEWANTHRAQUINONE DYEAND PROCESS OF MAKING SAME.

SPECIFICATION forming partof Letters Patent No. 734,866, dated July 28,1903.

Application filed May 2,1903. Serial No. 155,408- (No specimens.)

To aZZ whom it may concern.-

Be it known that we, EDUARD HEPP, Ph. D., residing atFrankfort-on-the-Main, and

. GHRIsTOPH HARTMANN, Ph. D., residing at Hochst-on-the-Main, Germany,both citizens A of the Empire of Germany, have invented certain new anduseful Improvements in the Q Manufacture of Dyestuffs of the Anthracenedin a coloring-matter is obtained which dyes A let shades.

chrome-mordanted or unmordanted wool vio- This. coloring matter has thecharacteristic property of being insoluble in A A NH,

We have found that by nitrating the anthraquinone ortho-sulfo acid andthen reducing I alpha-amido-anthraquinone sulfo-acid.

the products thus obtained two new amidoanthraquinone sulfo-acids areobtained, being sulfo-acid.

These amidoanthraquinone sulfo-acids when I treated with halogens andthen condensed with primary aromatic amins give new blue coloringmatters, being monosulfo acids,

which become very valuable if they are afterward sulfonated, and thustransformed into polysulfo-acids. The latter dye wool very pure blueshades and are also characterized by the property of being soluble inWater in presence of an excess of carbonate of soda or of caustic soda.

an aqueous solution containing an excess of carbonate of soda or ofcaustic soda. It is also known by the above-citedLetters Patent thatinstead of brominated alpha-amido-anthraquinone monosulfo-acid thecorresponding beta derivative can be employed or a mixture of the alphaand beta derivatives. By alpha and beta amidoanthraquinone sulfoacidsare evidently meant the acids which were first so designated by Claus(Ber. 01. cl. Chem. Ges. 15, page 1514) and prepared by reducing theproducts of nitration of the anthraquinone 1n eta-sulfo-acid. Thesesulfoacids were proved by being transformed into the correspondingdioxyanthraquinones to be 1: 6 and 1:7 derivatives having the followingformulae:

' I beta-amido-anthraqninone transformed in the usual manner intoanthrarufin and chrysazin and having, therefore, the formulae:

Ho s NE I I 1:5 amidoanthraquinone h I 1:8 amidoanthraquinone ulto (1Our invention may be carried out, for in stance, as follows: Ten parts,by weight, of I broinamidoanthraquinone sulfo acid (obtained by treatingamidoanthraquinone sulfoacid 1:5 with bromin) are mixed with one hundredparts of paratoluidin and the mixture is heated for about six hours to atemperature of to centigrade. The melt is then allowed to cool to about70 centigrade and poured into dilute hydrochloric acid. The sulfo-acidseparates out and is filtered. Itis transformed into sodium salt byboiling with a solution of carbonate of soda. The sodium salt thusobtained'is filtered and dried. To obtain the sodium salt of thepolysulfo-acids, ten parts of the sodium salt of monosulfo-acid aredissolved in one hundred parts of fuming sulfuric acid containing threeper cent. of S0 and the mixture is allowed to stand for some hours at atemperature of about 20 centigrade until a test portion of it dilutedwith water gives a precipitate of a sulfo-acid which is easily solublein carbonate of soda. The melt is then poured into water. Thecoloring-matter is precipitated by common salt and dried.

Similar coloring-matters are produced if for paratoluidin anilin orother primary aromatic amins are used and the products obtainedsubsequently sulfonated. Also for brominated amidoanthraquinonesulfo-acid 1: 5 the corresponding 1:8 derivative can be employed oramixture of the 1:5 and 1: 8 derivative.

The new coloring-matterdyes unmordanted and chrome-mordanted wool fastblue shades. When dry and pulverized, it is a dark-blue powder veryeasilysoluble in water, giving blue solutions easily precipitated bycommon salt, but not by an excess of carbonate of soda or of causticsoda. It dissolves in concentrated sulfuric acid with a feeble bluishtint, the color of the solution changing into red by the addition of asmall quantity of ice, While a larger quantity of ice produces a violetsolution and separates out a'blue precipitate. By the addition ofhydrochloric acid to the watery solution the color of the latter turnsviolet, and by the addition of ammonia to this solution the originalblue color is again produced.

Having now described our invention, what we claim is- 1. The process forproducing new anthraquinone dyestuffs, which consists in transformingthe condensation products obtained by heating halogenizedamidoanthraquinone sulfo-acids with an aromatic amin into polywhichdyestuflt's when dry and pulverized are dark powders easily soluble inwater with a blue color and also soluble in presence of an excess ofcarbonate of soda or of caustic soda,

dyeing unmordanted and chroine-mordanted wool fast blue shades.

4.. The herein-described specific new anthraquinone dyestuff obtainableby sulfonating the condensation product of brominated amidoanthraquinonesulfo acid 1: 5 with paratoluidin, being when dry and pulverized adark-blue powder easily soluble in water, giving thus blue solutionswhich are easily precipitated by common salt, but not by an excess ofcarbonate of soda or of caustic soda, the solution turning violet by theaddition of hydrochloric acid and assuming if neutralized with ammoniathe original blue color, soluble in concentrated sulfuric acid, yieldingsolutions showing a feeble bluish tint, the color of which turns firstred and then violet by adding ice, abluish precipitate being separatedout, dyeing unmordanted and chrome-mordanted wool fast blue shades.

In testimony that we claim the foregoing as our invention we have signedour names in presence of two subscribing witnesses.

EDUARD HEPP. OHRISTOPH HARTMANN. Witnesses:

ALFRED BRISBOIS, JOSEPH FLAOH.

